Copper complex compounds of trisazo dyestuffs



3,030,351 Patented Apr. 17, 1962 pyrazolone which may be sulfonated inthe aromatic 3,030,351 COPPER COMPLEX COMPOUNDS F nucleus. The couplingreactions are conducted in an TRESAZQ E FS alkaline, preferably sodaalkaline, medium; the second Albert Demagistri, Binningen, near Basel,Hans Ischer, coupling reaction may be carried out with the addition ofBasel, and Walter Wehrli, Riehen, near Basel, Switzerpyridine or amixture of pyridine bases. s f g g 's to Sandoz A.G., Basel,Switzerland, 3 Thecoppering of the new polyazo dyestuffs in substancewiss rm is carried out in such a way as to cause Splitting oif any p l iFiled ser'No'79367z alkoxy groups which may be present in ortho-positionClaims priority, application Switzerland May 2, 1955 to an azo groupExamples of Suitable coppepyielding 4 Claims. (Cl. 260-145) agents arecopper sulfate, copper acetate and copper The present application is acontinuation-in-part of the formate. application Ser. No. 580,978, filedApril 27, 1956, and The dyestuffs can be coppered, for example, byheating relates to copper containing polyazo dyestuffs of the withcopper salts in a weakly acid to alkaline medium, if formula desiredwith pressure and/or in the presence of ammonia wherein RO representsthe radical Z or the radical of a or organic bases, or in the suspensionof an alkali metal coupling component of the hydroxybenzene, hydroxysaltof a low molecular aliphatic monocarboxylic acid. naphthalene ofl-aryl-S-pyrazolone series coupled in The copper-containing polyazodyestuffs dye cotton ortho-position to -O-, in the nucleus A the azogrouping and fibers of regenerated cellulose in very level blue-grayN=N- stands in ortho-position to -O-. Acyl repto green-gray shades. Thebuilding-up properties on these resents the radical of a saturated orunsaturated lower fibers can easily be regulated by gradual addition ofsalts aliphatic monoor dicarboxylic acid, benzoic acid and its such assodium sulfate, chloride or carbonate, or by derivatives, e.g. loweralkyl-, lower alkoxy-, chlorine--, mixtures of such salts. In otherwords, the dyestuffs bromine-, nitroor sulfonic acid derivatives,cinnamic acid possess excellent salt-controllability, by virtue of whichand its derivatives, phenylacetic acid, phthalic acids and level, wellpenetrated dyeings are obtained, e.g. on crosstheir derivatives, 1-, orZ-naphthoic acid, furan-Z-carwound yarn packages, and shading with otherdyestuffs boxylic acid or cyclohexanecarboxylic acid, and n repreisfacilitated. The new dyestuffs also give penetrated dyesents one of theintegers 1 and 2, and whereby the dyeings on dead cotton. stuff moleculecontains at least three sulfonic acid groups. The fastness propertiesobtained with the new dyestuffs The process for the production of thecopper containing are excellent. The dyeing on natural and regeneratedpolyazo dyestufis consists in coupling 1 mol of the tetrazo cellulosefibers show very good fastness to light and to compound of4.4-diamino-3.3'-dimethoxy-l.1'-diphenyl wet treatments such as washing,water, perspiration, sea in either order with 1 mol of a monoazodyestuff, if desired water, wet pressing, water spotting, etc. Inaddition they in the form of its copper complex compound, having the arereadily dischargeable and fast to scropping, formaldegeneral formulahyde, alkalis and acids. The new dyestuffs give a very good reserve ofcellulose acetate, wool, silk, nylon, Perlon, acrylic and polyesterfibers. They show no appreciable change of shade on aftertreatment withresin crease-resisting agents and the dyeings retain excellent light andwet fastness properties after such finishing. The fastness to gas fumefading is also very good. The dyestuffs are insensitive to lime and onlyvery slightly sensitive to the metals iron, copper and chromium. Thefastness properties can be further improved by aftertreating the dyeingswith a polyalkylene-polyamine in presence of a copper salt or with apolyalkylene-polyamine containing copper O H O H NH-Acyl H0 8 N=N 0 all)n wherein n and Acyl have the previously defined meaning, and with 1 molof the same azo component or with 1 mol of a hydroxybenzene, ahydroxynaphthalene or a 1- aryl-S-pyrazolone coupling in ortho-positionto a phenolic in complex combination,

or enolic hydroxy group and treating subsequently the The followingexamples illustrate the invention. The polyazo dyestufi' so formed whichmust contain at least parts and percentages specified therein are byweight and three sulfonic acid groups, in substance with a copperthetemperatures are in degrees centigrade.

yielding agent.

The monoazo dyestuffs of general Formula II employed in the couplingreaction are applied preferably in the form of their copper complexcompounds. They may be coupled either in the first or second instancewith the tetrazotized 4.4 -diamino-3.3'-dimethoxy-1.1'-diphenyl. Thecoupling components corresponding to the radical R-O are preferablymonoazo dyestuffs if desired in the copperized or uncoppered form, ofthe Formula II, a hydroxybenzene, a hydroxynaphthalenemono-, diortrisulfonic acid, a dihydroxynaphthalenesulfonic acid or a l-aryl-S-Example I 24.4 parts of 4.4-diamino-3.3'dimethoxy-l.1-dipheny1 5 aresuspended in parts of water, 54 parts of concentrated hydrochloric acidand 150 parts of ice. A solution of 13.8 parts of sodium nitrite in 50parts of water is added to the suspension at 02. In order to prepare thediazomonoazo intermediate, the resultant tetrazo solution is run, at0-5", into a solution of 34.8 parts of sodium1-hydroxynaphthalene-3.8-disulfonate in 50 parts of water. ,After theaddition of a solution of 6 parts of sodium car- 150 parts of ice. At 2,there is added to the suspension a solution of 13.8 parts of sodiumnitrite in 50 parts of bonate in 30 parts of water, coupling on one sideto form the diazomonoazo compound takes place easily and quantitatively.For final coupling, there is added to the solu- Water, and stirringcontinued until the tetrazotization is tion of the intermediatecompound, at 5-10, a solution completed. To prepare the intermediatecompound, there of the copper complex compound from 61 parts of the 5 isadded to the tetrazo solution at 5 a solution of the monoazo compound ofthe formula copper complex compound from 61 parts of the monoazodyestufi of the formula OH HO OH HO HO S HO S W00 H6 H0 in 350 parts ofwater, 10 parts of 30% aqueous caustic in 700 parts of pyridine and 700parts of water, after soda solution and 50 parts of aqueous sodiumcarbowhich 100 parts of concentrated aqueous ammonia are nate solution.Then 50 additional parts of 20% aqueous added to the resultant mixture.Upon completion of the sodium carbonate solution are added to thecoupling mixcoupling, the obtained trisazo dyestutt is salted out of the20 ture. Coupling on one side takes place easily and quansolution and isfiltered ofi'. titatively.

For demethylating coppering of the trisazo dyestuff, For final coupling,there is added to the mixture a the obtained filter cake is stirred into4000 parts of water, solution of 33.4 parts of1-phenyl-3-rnethyl-5-pyrazolone- 50 parts of diethanolamine are added tothe suspension, 2,4-disulfonic acid in 125 parts of water and 100 partsand the latter then heated to 80. At 8090, there is of 20% aqueoussodium carbonate solution. Upon comrun thereinto, in the course of ahalf hour, a solution of pletion of the coupling, the resultant trisazodyestutf is 50 parts of crystalline copper sulfate and 70 parts ofsalted out and is filtered off. concentrated aqueous amomnia in 300parts of water. Demethylating coppering of the said trisazo dyestuff isAs a result, the trisazo dyestuff goes into solution; the carried outafter manner described in Example 1. The solution is then stirred for 20hours at 9597. The copso-obtained copper-containing trisazo dyestuffwhich corper-containing trisazo dyestutf which is thus formed isresponds to the formula then salted out of the solution, filtered OE anddried. It corresponds to the formula is a dark powder which dissolveswith blue-green coloration in water and which dyes cotton and fibers ofregenerand is a dark powder which dissolves with blue coloration atedcellulose in fast green-gray shades.

in water and with blue-green coloration in concentrated The followingtable sets forth additional copper-consulfuric acid, and dyes cotton andfibers of regenerated taining polyazo dyestuffs which can be preparedaccordcellulose in fast blue-gray shades. ing to the manner set forth inExamples 1 and 2. These 0.1 part of copper-containing trisazo dyestuifis dis additional dyestufis possess, in the unmetallized state,

solved in 300 parts of lime-free water. In the so-prepared the formulabath, 10 parts of prewetted cotton fabric are dyed, the

bathbeginning at a temperature of 30being heated to boiling in thecourse of 30 minutes and then being maintained in the vicinity of theboiling temperature for 15 11 minutes. 3 to 4 parts of sodium sulfate,in the form of E035 a 10% aqueous solution, are added portionwise to thebath l HO during the dyeing process. The dyed material is allowed O tocool in the bath to 50 in the course of 15 to 20 minutes, after which itis withdrawn, washed with water, centrifuged and dried. After-treatmentof the so-obtained dyed material, according to US. Patent No. 2,622,075(Examples 7 and 11), with a cation-active copper complex compound, whichmay be basic in character, e.g. with a copper-containing polyalkylenepolyamine, produces a distinct improvement in the fastness properties ofthe dyeing. I

p Example 2 In column C by the second azo component which forms 31.7parts of 4,4'-diamino-3,3'-dimethoxy-1,1-diphenyl the radical R andhydrochloride are stirred into a mixture of 250 parts of In column D bythe shade of the copper containing dyewater, 35.5 parts of concentratedhydrochloric acid and 0 ing of the polyazo dyestuff on cotton.-

(Ill).

and are characterized in the table:

In column B by the Acyl amino-hydroxynaphthalenemono or di-sulfonic acidon which the azo component R of Formula III is based;

Example 82 OO O NH-C OCH=CH o--cu Having thus disclosed the inventionwhat is claimed is: 10 group consisting of chloro, bromo, methoxy,ethoxy,

1. A dyestuff of the formula methyl, nitro and sulfo, and X is a memberselected from I NH-Acyl soar: -N=N (Hots)m $0 11 [I ,I X

0o 1 0-041 6 wherein m is an integer ranging from 1 to 2, Acyl is a 20the group consisting of hydrogen and hydroxy. member selected from thegroup consisting of the radi- 2. The copper complex dyestuif whichcorresponds to cals of unsubstituted benzene monoand di-carboxylic theformula 0 Cu-O NIH-CO0 -soan Hms- N:-

I I H03 o-oi1 8-041 OaH acids and substituted benzene monoanddi-carboxylic 3. The dyestuff of the formula H035 o-ou-0 O( 3u-O I -l$I=N- Hots- -so,H HOnS- N= N- -NHO CO I -oi1 acids, the substituents ofwhich are selected from the 4. The dyestufi of the formula H0 8 OCu oReferences Cited in the file of this patent UNITED STATES PATENTS2,644,813 Ruckstuhl July 7, 1953 UNITED STATES PATENT OFFICE CERTIFICATEOF CORRECTION Patent No. 3,030,351 April 17, 1962 Albert Demagistri eta1.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 1, line 29, for "of" read or column 2, line 44', for "scropping"read scrooping column 3, line 27, for "amomnia" read ammonia columns 5and 6, in the table, under the heading (B), Item 31, for "2,benzoylaminoread 2-benzoylamino same table, columns 7 and 8, under the heading (C),Item 73, for "-hydroxynaphtahlene" read -hydroxynaphthalene same columns7 and 8, Example 4, lower right-hand portion of the formula, for

I 5030 read SO3H same columns, Example 81, the central moiety of theformula should appear as shown below instead of as in the patent:

columns 9 and 10, claim 2, left-hand portion of the formula, for "-N NIread -N==N Signed and sealed this 6th day of November 1962.

(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patent-s

1.A DYESTUFF OF THE FORMULA